Fixation of pigments on textile materials



Patented July 5, 1949 UNITED STATES PATENT OFFICE 2,414,960 FIXATIQNOFMIg gEMIENTALg N TEXTILE Henry Charles Olpin, Philip Broughton Law,and

Sydney Alfred Gibson, England, assignors, .by'

Celanese Corporation of America,

of Delaware Spondon, near Derby,

mesne assignments, to

a corporation No Drawing. Application May a, 1945,

Serial No. 592.120

2 Claims. (01. 111-401) ment so that it resists removal by washing anddoes not dust ofi and further that the adhesive should be colourless andshould not materially ailfect the handle of the textile materials.Moreover the adhesive and any treatment necessary to render iteffective, for example steaming or heating, should not be such as todamage the fabric. Albumen has commonly been employed as an adhesive forthe foregoing purpose, the material being printed with a preparationcomprising the pigment and a suitable albumen (usually eg-g albumen) andthen steamedto render the albumen employed insoluble in water. Thealbumens. I suitable for use in this process are somewhat variable inquality and price and tend to stiiifenthe fabrics unduly. Varioussynthetic resins derived from formaldehyde have been tried in place ofalbumen, the resin being applied to the fabric in water-soluble form andthen converted into an insoluble form by heating. However many suchresins develop colour during the heating and others require for theirinsolubilisation temperatures so high as to involve risk of damagingtextile materials. Temperatures much above 100 C. are further notconveniently attainable in the machines commonly available in textileprinting works.

We have now found that the condensation products of formaldehyde orother aliphatic aldehydewith substitution products, of biguanide areparticularly efiective for fixing pigments on textile material. Thus athickened preparation containing titanium dioxide, and a water-solublecondensation product of formaldehyde and ethylene' di-biguanide can beprinted on a lustrous fabrlc of artificial filaments and .then heated toinsolubilise the condensation product. The titanium dioxide is wellfixed and forms a dull pattern on a lustrous ground. Fixation can beefiected at a low temperature, for example as low as 90' C. and thematerial has a soft handle.

The substitution products of biguanides can be alkyl, aralkyl,cyclo-alkyl, or aryl substitution products, and include compounds inwhich more than one biguanide radicle is attached to a single organicresidue as in alkylene-di-biguanides. Such substituted biguanides can beobtained by the action of dicyandiamide on the hydrochloride of theappropriate alkyl-, aralkyl-, cyclo-alkylor aryl-amine. Primary orsecondary amines can be used. Thus mono-biguanides can be obtained fromdicyandiamide and ethylamine, di-ethylamine, hydroxyethylamine,propylamine, butylamine, .Z-hydroxy-propylamine, benzylamine, aniline,toluldines, and methoxy-anilines, and di- 'biguanides fromethylene-diamine, alpha-betadiamino-propane,. trimethylene diamine, andhexamethylene diamine and other alkylene diamlnes. I

The reaction between dicyandiamide and an amine hydrochloride isconveniently effected by heating at temperatures of the order of -200 C.It appears that the reaction often proceeds, at least in part, beyondthe formation of the simple biguanide radicle since some ammonia isgiven ofi. Possibly two biguanide radicles lose ammonia with formationof a polyguanide radicle such as II NH NH NH NH The biguanidederivatives obtainable by heating hydrochlorides of amines withdicyandiamide are well suited for use according to the invention.

For the purposes of the present invention the biguanide derivatives arebest converted into water-soluble condensation products by reaction withformaldehyde, acetaldehyde or other allphaticaidehyde. Formaldehyde isthe preferred aldehyde and may be used in the form of 25 to 40 per centaqueous solutions to react with. the biguanide derivative; furtheradditions are usually not essential.

The water-soluble condensation product is then applied to the textilematerial in conjunction with the pigment to be fixed. The preparationapplied to the fabric may be thickened with one of the thickenersusually employed in the preparation of textile printing pastes, forexample gum tragacanth. Further it may contain an acid or othersubstance capable for promoting the conversion of the water-solublecondensation product to a water-insoluble product on heating. Solidhydroxy aliphatic acids such as tartaric acid, citric acid, lactic acid,and other dimcultly volatile or non-volatile organic acids are suitablefor this purpose. Again, weak inorganic acids such as boric acid may beused.

The application of the compositions containing the water-solublecondensation product and pigment to textile materials can be efl'ectedin various ways, the choice depending on the eifects required. Thus theycan be applied locally by printing or stedncilling methods in anydesired patterns. Again they may be applied to the whole surface of thefabric. e. g. by "all over printing with an engraved roll.

Conversion of the water-soluble condensation product to water-insolubleform on the material can be effected by heating the material.Temperatures of 80 C. to 130 C. can be used though a temperature ofabout 90 C. is often sufficient. The heating can be eifected by passingthe textile material through an oven at the requisite tem- '4 centstrength; after cooling, 2.7 parts of tartaric acid are then added. Theresulting solution is stable, no precipitate forming on standing forseveral days. The following printing paste is then prepared: I

' Parts Gum tragacanth (6%) (not neutralised) 50 The above solution 8Titanium dioxide (50% aqueous paste) 15 Water 27 A lustrous celluloseacetate satin fabric is printed perature. Again it can be efiected on anordinary stentering machine, the temperatures of 80 C(to 100 C. readilyattainable with these machines usually suflicient to insolubilise thecondensation product. The duration of the heating may be 2 to 10minutes.

After the heating the material is preferably rinsed and soaped to removethickening agent and other unwanted matter.

The process is particularly useful for fixing white pigments on textilematerials, for example titanium dioxide or barium sulphate. Colouredpigments may be similarly fixed, for example inorganic pigments, e. g.Prussian blue, ultramarine, lead chromate, cadmium chromate, or ironoxide, or organic pigments, e. g. phthalocyanine dyes, vat dyes andwater-insoluble azo dyes having little or no direct affinity for textilematerials.

Various textile materials whether of natural or artificial fibres mayhave pigments fixed on them by the new process. The textile material maybe of fibres of natural silk, natural or regenerated cellulose, orcellulose acetate or other cellulose ester or ether. Fixation of whitepigments is of greatest value on lustrous textile fabrics of artificialfibres, by reason of the attractive effects which can be obtained. Suchartificial fibres may be continuous filaments of regenerated cellulosespun by the viscose or cuprammonium process or obtained bysaponification of cellulose ester fibres which have been stretched, e.g. in steam or hot water. Again the treatment may be applied to lustroustextile fabrics of continuous filaments of cellulose acetate or othercellulose ester or ether, e. g. cellulose propionate, butyrate,acetopropionate, or acetobutyrate, or of ethyl cellulose or other etherof cellulose.

The invention is illustrated by the following example in which the partsreferred to are parts by weight:

Example 4 parts of ethylene diamine hydrochloride and 5 parts ofdicyandiamide are melted together at 120 C. to 140 C. and thetemperature-slowly raised to 200 C. which is maintained for 7 hoursduring which time ammonia is evolved. 18 parts of the product are warmedto 70 C. for 1 hour with 33 parts of aqueous formaldehyde of 40 per withthis paste and then passed through a stenter at a temperature of C., thetime of passage being 3 minutes.

a cold water for 30 minutes, soaped in a 0.5 gram The material is thenrinsed in per litre soap solution for 10 minutes at 40 C., and finallyagain rinsed.

A pure white dull pattern on a lustrous ground is obtained which isexceedingly resistant to washing. Moreover the outlines of the patternare sharp and the fabric has a soft handle and is free from theundesirable "boardiness and cockling often associated with albumenprints.

By replacing the ethylene diamine hydrochloride by an equivalent amountof hexamethylene diamine hydrochloride similar results can be obtained.

Having described our invention, what we desire to secure by LettersPatent is:

1. A process for fixing pigments on artificial textile material, whichcomprises applying to the material an aqueous paste, comprising thepigment, an organic acid of low volatility and a water-solublecondensation product of formaldehyde and a substitution product ofbiguanide obtainable by heating dicyandiamide with ethylene diaminedihydrochloride to -200 C., and then heating the material to atemperature of 80-100 C.

2. Textile materials made up of continuous artificial filament yarns andhaving a pigment fixed thereon by means of a water-insolublecondensation product of formaldehyde and a substitution product ofbiguanide obtainable by heating dicyandiamide with ethylene diaminedihydrochloride to 150-200 C.

HENRY CHARLES OLPIN. PHILIP BROUGHTON LAW. SYDNEY ALFRED GIBSON.

REFERENCES CITED The following references are of record in'the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,123,152 Rivat July 5, 19382,169,546 Widmer Aug. 15, 1939 2,222,350 Keller et al Nov. 19, 19402,248,696 Cassel July 8, 1941 2,287,597 Brookes June 23, 1942 2,304,113Morgan Dec. 8, 1942 2,334,545 DAlelio NOV. 16, 1943 2,405,863 TrebouxAug. 13, 1946 2,418,696 Cameron Apr. 8, 1947

